JPH01124919A - Manufacture of oxide superconductor - Google Patents
Manufacture of oxide superconductorInfo
- Publication number
- JPH01124919A JPH01124919A JP62283628A JP28362887A JPH01124919A JP H01124919 A JPH01124919 A JP H01124919A JP 62283628 A JP62283628 A JP 62283628A JP 28362887 A JP28362887 A JP 28362887A JP H01124919 A JPH01124919 A JP H01124919A
- Authority
- JP
- Japan
- Prior art keywords
- film
- forming
- gas
- oxide
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000000034 method Methods 0.000 claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 230000001678 irradiating effect Effects 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 abstract description 31
- 239000007789 gas Substances 0.000 abstract description 28
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 238000010884 ion-beam technique Methods 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 229910052786 argon Inorganic materials 0.000 abstract description 5
- 238000001771 vacuum deposition Methods 0.000 abstract description 4
- 230000001133 acceleration Effects 0.000 abstract description 3
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- 229910052740 iodine Inorganic materials 0.000 abstract description 3
- 238000001451 molecular beam epitaxy Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 35
- 239000000463 material Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 239000012528 membrane Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Vapour Deposition (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
この発明は、例えばジョセフソン素子、超電導記憶素子
などの超電導デバイス、超電導マグネット用コイルなど
に使用可能な酸化物系超電導体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing an oxide-based superconductor that can be used for superconducting devices such as Josephson elements and superconducting memory elements, coils for superconducting magnets, and the like.
［従来の技術］
近時、常電導状態から超電導状態に遷移する臨界温度（
Ｔｃ）が液体窒素温度以上の高い値を示す酸化物系の超
電導体が種々発見されつつある。[Prior art] Recently, the critical temperature at which the normal conductive state transitions to the superconducting state (
Various oxide-based superconductors are being discovered that exhibit Tc) values higher than the liquid nitrogen temperature.
現在のところ、このような酸化物系超電導体を製造する
方法としては、例えば、真空蒸着法、スパッタリング法
、分子線エピタキシー（ＭＢＥ）法、化学気相成長（Ｃ
ＶＤ）法、イオン気相成長（ＩＶＤ）法などの成膜法が
知られている。そして、このような成膜法においては、
いずれの場合も、例えばＩＴｏｒｒ以下の低圧下で、か
つ酸素ガス雰囲気あるいは酸素ガスと不活性ガスとの混
合ガス雰囲気、中で酸化物系超電導体からなる膜体を製
造することができる。しかし、このままでは、成膜時・
の雰囲気中の酸素分圧か低いことから、基体上に形成さ
れる膜体の結晶中に所望量の酸素が導入されにくく、そ
の結晶組成が化学量論的組成からずれてしまうため、臨
界温度（Ｔｃ）や臨界電流密度（Ｊｃ）や臨界磁界（Ｈ
ｅｌ）などの超電導特性が低い膜体が生成される傾向が
あり、このため、成膜後に酸素雰囲気中で高温熱処理（
例えば、８００℃〜１，０００℃）を行なうことによっ
て、上記膜体の結晶中に酸素を所望量導入して膜体の超
電導特性を改善する試みがなされている。At present, methods for producing such oxide-based superconductors include, for example, vacuum evaporation, sputtering, molecular beam epitaxy (MBE), and chemical vapor deposition (C
Film forming methods such as VD) method and ion vapor deposition (IVD) method are known. In such a film formation method,
In either case, a film body made of an oxide-based superconductor can be produced under a low pressure of, for example, ITorr or less and in an oxygen gas atmosphere or a mixed gas atmosphere of oxygen gas and an inert gas. However, if this continues, the film formation time and
Due to the low oxygen partial pressure in the atmosphere, it is difficult to introduce the desired amount of oxygen into the crystals of the film formed on the substrate, and the crystal composition deviates from the stoichiometric composition. (Tc), critical current density (Jc), critical magnetic field (H
There is a tendency for film bodies with low superconducting properties such as
For example, attempts have been made to improve the superconducting properties of the membrane by introducing a desired amount of oxygen into the crystals of the membrane by heating the membrane at a temperature of 800 DEG C. to 1,000 DEG C.).
［発明が解決しようとする問題点］
しかしながら、上記従来の方法にあっては、いずれの場
合も基体温度が７００℃以下では、膜体がアモルファス
となり超電導を示さない。したがって成膜時、基体温度
を７００℃以上に設定する必要があるが、この場合、成
膜後の酸素雰囲気中での高温熱処理と併せて、以下のよ
うな不都合が指摘されている。[Problems to be Solved by the Invention] However, in any of the above conventional methods, when the substrate temperature is 700° C. or lower, the film becomes amorphous and does not exhibit superconductivity. Therefore, it is necessary to set the substrate temperature to 700° C. or higher during film formation, but in this case, the following disadvantages have been pointed out in addition to high-temperature heat treatment in an oxygen atmosphere after film formation.
（１）基体温度の高温設定や高温熱処理により膜体の構
成元素が基体の構成元素と反応して両者の界面に化合物
が生成され易く、このため良好な超電導特性を示す酸化
物系超電導体からなる膜体を得ることが難しい。(1) Due to the high temperature setting of the substrate or high-temperature heat treatment, the constituent elements of the film react with the constituent elements of the substrate, and compounds are likely to be generated at the interface between the two, and for this reason, oxide-based superconductors exhibit good superconducting properties. It is difficult to obtain a film body that looks like this.
（２）上記（１）の場合において、膜体の構成元素と反
応しにくい基体（酸化マグネシウム（ＭｇＯ）、チタン
酸ストロンチウム（Ｓ ｒＴ ｉＯｓ”）も存在するが
、これらは高価である。(2) In the case of (1) above, there are also substrates (magnesium oxide (MgO), strontium titanate (S rTiOs)) that are difficult to react with the constituent elements of the film body, but these are expensive.
（３）ジタセフソン素子などの微細加工を必要とする素
子を製造する場合、基体温度の高温設定や高温熱処理に
より微細加工部分に欠陥が生じ易く、高度に集積化した
素子を製造することが難しい。(3) When manufacturing devices that require microfabrication, such as Jitasefson devices, defects tend to occur in microfabricated parts due to high temperature setting of the substrate temperature or high temperature heat treatment, making it difficult to manufacture highly integrated devices.
このような事情から、従来より、基体温度の高温設定ま
たは高温熱処理を施さずとも、良好な超電導特性を示し
得る酸化物系超電導体の製造技術の開発が望まれている
。Under these circumstances, it has been desired to develop a manufacturing technology for oxide-based superconductors that can exhibit good superconducting properties without setting the substrate temperature at a high temperature or performing high-temperature heat treatment.
そこで、この発明にあっては、酸化物系超電導体あるい
は酸化物系超電導体の前駆体を成膜法により形成する際
に、非還元性ガスを加速して照射しつつ形成することに
より上記問題点を解決した。Therefore, in the present invention, when forming an oxide superconductor or a precursor of an oxide superconductor by a film forming method, the above problem is solved by forming the oxide superconductor or a precursor of the oxide superconductor while accelerating irradiation with a non-reducing gas. Resolved the point.
以下、この発明の酸化物系超電導体の製造方法を詳しく
説明する。Hereinafter, the method for producing an oxide-based superconductor of the present invention will be explained in detail.
この発明では、第１図に示すように基体ｌを用意する。In this invention, a base 1 is prepared as shown in FIG.
この基体ｌには、例えば板材、線材、テープ材、筒状体
、柱状体など種々の形状のものが用いられる。そして、
このような基体１の形成材料としては、比較的安価な材
料、例えばステンレス、アルミニウム、銅などの金属材
料、これらの合金材料、上記金属または合金材料の窒化
物や炭化物、安定化ジルコニア、アルミナ、シリコン、
シリカ、ニオブ酸リチウム、サファイア、ルビーなどの
結晶材料が用いられる。The base 1 may be of various shapes, such as a plate, a wire, a tape, a cylinder, or a column. and,
Examples of materials for forming the base 1 include relatively inexpensive materials, such as metal materials such as stainless steel, aluminum, and copper, alloy materials thereof, nitrides and carbides of the above-mentioned metals or alloy materials, stabilized zirconia, alumina, silicon,
Crystalline materials such as silica, lithium niobate, sapphire, and ruby are used.
次いで、このような基体１上に酸化物系超電導体あるい
はその・前駆体からなる膜体２を形成する。Next, a film body 2 made of an oxide superconductor or its precursor is formed on such a substrate 1.
ここで酸化物系超電導体としては、典型的にはＡ−Ｂ−
Ｃ−Ｄ系（ただし、ＡはＹ、Ｓｃ、Ｌａ、Ｃｅ。Here, the oxide superconductor is typically AB-
CD system (A is Y, Sc, La, Ce.
Ｐｒ、Ｎｄ、Ｐｓ、Ｓｓ＋、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、
Ｈｏ、Ｅｒ、Ｔｍ。Pr, Nd, Ps, Ss+, Eu, Gd, Tb, Dy,
Ho, Er, Tm.
Ｙｂ、Ｌｕの周期律表第ｍａ族元素のうち１種あるいは
２種以上を表し、ＢはＳｒ、Ｂａ、Ｃａ、Ｂｅ、Ｍｇ。Yb and Lu represent one or more elements of group ma of the periodic table, and B represents Sr, Ba, Ca, Be, and Mg.
Ｒａの周期律表第１［ａ族元素のうち１種あるいは２種
以上を表し、ＣはＣｕ、Ａｇ、Ａｕの周期律表第ｉｂ族
元素とＮｂ元素のうちＣｕあるいはＣｕを含む２種以上
を表し、ＤはＯ，Ｓ、Ｓｅ、Ｔｅ、Ｐｏの周期律表第ｖ
＋ｂ族元素及びＦ、ＣＩ２．Ｂｒ、Ｉ’、Ａｔの周期律
表第■ｂ族元素のうち０あるいは０を含む２種以上を表
す。）のものが用いられる。そして、この酸化物系超電
導体の各構成元素の組成は、例えばＹ−Ｂａ−Ｃｕ−０
系超電導体の場合、Ｙ ： １ 、Ｂａ； ２〜３．Ｃ
ｕ； ３〜４．０ ；７−δとされ、また、δはＯ≦δ
≦５の範囲とされる。なお、上記°酸化物系超電導体の
前駆体は、上記Ａ−Ｂ−Ｃ−Ｄ系超電導体の組成に比べ
てその構成元素の酸素の一部が欠損して、その超電導特
性が芳しくないものである。Ra represents one or more of the Group A elements of the Periodic Table 1 [A], and C represents Cu or two or more of the Group Ib elements of the Periodic Table of Cu, Ag, and Au and the Nb element; , D represents the periodic table v of O, S, Se, Te, Po.
+b group elements and F, CI2. Represents 0 or two or more elements containing 0 among the elements of Group 1b of the periodic table, such as Br, I', and At. ) are used. The composition of each constituent element of this oxide superconductor is, for example, Y-Ba-Cu-0
In the case of a system superconductor, Y: 1, Ba; 2-3. C
u; 3-4.0; 7-δ, and δ is O≦δ
The range is ≦5. In addition, the precursor of the above-mentioned oxide-based superconductor is one in which a part of the constituent element oxygen is deficient compared to the composition of the above-mentioned A-B-C-D-based superconductor, and its superconducting properties are poor. It is.
また、上記膜体２の形成方法としては、例えば真空蒸着
法、スパッタリング法、分子線エピタキシー（ＭＢＥ）
法、化学気相成長（ＣＶＤ）法、イオン気相成長（ＩＶ
Ｄ）法などの成膜法にイオンビームアシスト法を組合わ
せた方法が好適に用いられる。このイオンビームアシス
ト法は、成膜時に、ガスイオンを対象物（形成中の膜体
２）に加速して照射し、膜体２の膜質を向上させる方法
であるが、この発明で使用されるガスイオンは非還元性
ガスである。ここで非還元性ガスとは、Ａ ｒ、 Ｈｅ
。Further, as a method for forming the film body 2, for example, a vacuum evaporation method, a sputtering method, a molecular beam epitaxy (MBE), etc.
method, chemical vapor deposition (CVD) method, ion vapor deposition (IV
A method in which an ion beam assist method is combined with a film forming method such as method D) is preferably used. This ion beam assist method is a method in which gas ions are accelerated and irradiated onto the target object (the film body 2 being formed) during film formation to improve the film quality of the film body 2, and is used in this invention. Gas ions are non-reducing gases. Here, non-reducing gases include Ar, He
.
Ｎｅ、Ｘｅなどの不活性元素、Ｆ、Ｃ１，Ｂｒ、Ｉなど
のハロゲン元素、及び窒素元素のうち、単独あるいは２
種以上を含むイオン、原子、または分子の気体を指称す
るものである。Inert elements such as Ne and Xe, halogen elements such as F, C1, Br, I, and nitrogen elements alone or in combination
Refers to a gas containing more than one species of ions, atoms, or molecules.
そして、上記イオンビームアシスト法は、前述の成膜法
のいずれかと任意に組合わせることが可能であるが、こ
こで、−例（実施態様）として、真空蒸着法とイオンビ
ームアシスト法との組合わせによる膜体２の形成方法に
ついて第２図を参照しながら説明する。The ion beam assist method described above can be arbitrarily combined with any of the film forming methods described above, but here, as an example (embodiment), a combination of the vacuum evaporation method and the ion beam assist method is used. A method of forming the film body 2 by lamination will be explained with reference to FIG. 2.
第２図は、この発明に用いられる製造装置の一例を示す
ものである。図中符号３で示されるこの製造装置は、真
空蒸着装置にイオンビームアシスト用のイオン源４を追
加して設けてなるものであり、具体的には、この製造装
置３は、非還元性ガスイオンを加速して対象物（形成中
の膜体２）に照射するイオン源４と、基体ｌを保持する
板状の基体ホルダ５と、この基体ホルダ５に所定間隔を
もって対向する三つのるつぼ６．６．６とから概略構成
されている。そして、イオン源４は基体ホルダ５に基体
ｌを保持した場合に、基体ｌ上の膜体２に向くように配
設されている。ま、た基体ホルダ５は電気的に接地され
ている。さらに、上記三つのるつぼ６，６．６のそれぞ
れの近傍には、蒸着材料に電子ビームを直接あてて加熱
するようにした電子銃７．７．７が設けられている。FIG. 2 shows an example of a manufacturing apparatus used in the present invention. This manufacturing device, indicated by the reference numeral 3 in the figure, is a vacuum evaporation device with an ion source 4 for ion beam assist added thereto. Specifically, this manufacturing device 3 uses non-reducing gas. An ion source 4 that accelerates ions and irradiates the target object (film body 2 being formed), a plate-shaped substrate holder 5 that holds a substrate 1, and three crucibles 6 that face the substrate holder 5 at predetermined intervals. It is roughly composed of .6.6. The ion source 4 is arranged so as to face the membrane 2 on the substrate 1 when the substrate 1 is held in the substrate holder 5. Furthermore, the substrate holder 5 is electrically grounded. Further, in the vicinity of each of the three crucibles 6, 6.6, an electron gun 7.7.7 is provided which heats the vapor deposition material by directly applying an electron beam to it.
このような構成の製造装置３を用いて膜体２を形成する
にあたっては、まず、基体ホルダ５に基体ｌを取り付け
ると共に、膜体２の形成材料（蒸着材料）をるつぼ６．
６．６に入れる。ここで、膜体２の形成材料としては前
述したＡ−Ｂ−Ｃ−Ｄ系超電導体を構成する元素を含む
ものが用いられる。例えば、上記Ａ−Ｂ−Ｃ−Ｄ系の超
電導体の構成元素Ａ、Ｂ、Ｃの単体または酸化物、例え
ばＹ。When forming the film body 2 using the manufacturing apparatus 3 having such a configuration, first, the base body 1 is attached to the base body holder 5, and the material for forming the film body 2 (evaporation material) is placed in the crucible 6.
6. Put it in 6. Here, as the material for forming the film body 2, a material containing the elements constituting the above-mentioned A-B-C-D superconductor is used. For example, simple substances or oxides of constituent elements A, B, and C of the above-mentioned A-B-C-D superconductor, such as Y.
Ｂａ、Ｃｕをそれぞれ別々のるつぼ６．６．６に入れる
。そして、上記イオン源４と基体ホルダ５と三つのるつ
ぼ６，６．６とを共に低圧の酸素雰囲気下におくように
する。このような状態の下で、まず、基体ｌをヒータ（
図示せず）により６００℃〜７００℃に予熱する。次ぎ
に、電子銃７．７．７から３源同時に電子ビームを発生
させ、これにより発生した電子ビームをるつぼ６．６．
６内の膜体２の形成材料に衝突させ、この衝突により加
熱された形成材料の中性原子や分子を蒸発させて基体１
表面に堆積させて膜体２を形成する。Put Ba and Cu into separate crucibles 6.6.6. Then, the ion source 4, substrate holder 5, and three crucibles 6, 6.6 are placed together in a low pressure oxygen atmosphere. Under these conditions, first, the substrate l is placed in a heater (
(not shown) to 600°C to 700°C. Next, three sources of electron beams are simultaneously generated from the electron guns 7.7.7, and the electron beams thus generated are transferred to the crucibles 6.6 and 7.
The neutral atoms and molecules of the forming material heated by this collision are evaporated to form the base 1.
A film body 2 is formed by depositing it on the surface.
そして、この膜体２の形成に伴って、イオン源４の先端
部に設けられた加速電極（図示せず）により非還元性ガ
スイオンを所定の速度に加速し、加速された非還元性ガ
スイオンを基体ｌの表面に照射すると共に、雰囲気中の
酸素に衝撃を与えてこれを活性化（イオン化あるいは原
子化）する。As the film body 2 is formed, non-reducing gas ions are accelerated to a predetermined speed by an accelerating electrode (not shown) provided at the tip of the ion source 4, and the accelerated non-reducing gas Ions are irradiated onto the surface of the substrate 1, and oxygen in the atmosphere is bombarded to activate (ionize or atomize) it.
また、非還元性ガスイオンにより活性化された酸素も基
体ｌの表面に照射される。ここで、上記の加速電極に印
加される電圧は、膜体２内に照射される際の非還元性ガ
スイオンなどの衝突速度、イオン源４と基体ｌとの離間
寸法、真空蒸着条件などに応じて適宜法められる。また
、加速により非還元性ガスイオンに与えられるエネルギ
ーはｌＯ〜２０００ｅＶの範囲であることが望ましい。Furthermore, oxygen activated by non-reducing gas ions is also irradiated onto the surface of the substrate l. Here, the voltage applied to the accelerating electrode mentioned above depends on the collision speed of non-reducing gas ions etc. when irradiating the inside of the film body 2, the distance between the ion source 4 and the substrate l, the vacuum evaporation conditions, etc. Laws will be enacted accordingly. Further, it is desirable that the energy given to the non-reducing gas ions by acceleration is in the range of lO to 2000 eV.
１０ｅＶ未満では、エネルギー不足で非還元性ガスイオ
ンなどが膜体２内に注入されにくく、２０００ｅＶを越
えると、非還元性ガスイオンの注入効果が頭打ちとなり
、不経済である。If it is less than 10 eV, it is difficult to inject non-reducing gas ions into the membrane body 2 due to lack of energy, and if it exceeds 2000 eV, the effect of non-reducing gas ion injection reaches its peak, which is uneconomical.
この上うな成膜法により製造された膜体２は、非還元性
ガスイオンを用いた上記イオンビームアシスト法の効果
により、膜体２を構成する各元素が適度に活性化される
ので、結晶のＣ軸が基体ｌの垂直方向に配向した膜体２
を得ることができ、したがって、全体が均質でＪ−段と
良好な超電導特性を得ることができると共に、基体１と
の付着が強固な膜体を形成することができる。また、上
記イオンビームアシスト法によれば、従来の成膜法に比
べて膜体２の結晶中への酸素の導入量が増加することが
確認された。したがって、酸化物超電導体の前駆体から
なる膜体２によれば、成膜後の酸素雰囲気中での熱処理
を低温下で行って、最終物質（酸化物超電導体からなる
膜体２）を製造することができる。したがって、以上の
製造方法によれば、さらに、次のような優れた効果を得
ることができる。すなわち、従来法と異なり、成膜時の
基体温度及び成膜後の熱処理温度を低温に設定すること
ができるので、（１）基体ｌと膜体２とが高温で反応し
合う不都合もなく、この点においても膜体２の超電導特
性を良好なものとすることができる。（２）基体ｌの形
成材料として比較的安価な材料を選ぶことができる。（
３）微細加工部分に熱的欠陥が生Ｅにくいため、例えば
ジョセフソン素子など、微細な超電導デバイスを一段と
良好に製造することができる。Moreover, the film body 2 manufactured by this film-forming method is crystallized because each element constituting the film body 2 is appropriately activated by the effect of the above-mentioned ion beam assist method using non-reducing gas ions. A film body 2 whose C axis is oriented perpendicular to the substrate l.
Therefore, it is possible to obtain a homogeneous overall superconducting property with good J-level superconducting properties, and also to form a film body with strong adhesion to the substrate 1. Furthermore, it was confirmed that according to the ion beam assisted method, the amount of oxygen introduced into the crystal of the film body 2 was increased compared to the conventional film forming method. Therefore, according to the film body 2 made of a precursor of an oxide superconductor, the final material (film body 2 made of an oxide superconductor) is manufactured by performing heat treatment in an oxygen atmosphere at a low temperature after film formation. can do. Therefore, according to the above manufacturing method, the following excellent effects can be obtained. That is, unlike the conventional method, the substrate temperature during film formation and the heat treatment temperature after film formation can be set to low temperatures, so (1) there is no inconvenience that the substrate 1 and the film body 2 react with each other at high temperatures; Also in this respect, the superconducting properties of the membrane body 2 can be made good. (2) A relatively inexpensive material can be selected as the material for forming the base 1. (
3) Since thermal defects are less likely to occur in microfabricated parts, microscopic superconducting devices such as Josephson elements can be manufactured even better.
なお、上記の例では、前述の成膜法により基体ｌ上に膜
状の膜体２を形成するようにしたが、成膜する際の製造
方法、製造条件を選ぶことで基体ｌ上に粉末状あるいは
微粉末状あるいは超微粒子状の酸化物系超電導体を形成
することができる。In the above example, the film-like film body 2 was formed on the substrate l by the above-mentioned film-forming method. It is possible to form an oxide-based superconductor in the form of a powder, a fine powder, or an ultrafine particle.
したがって、この場合にも、上記の例と同様に成膜中に
イオンビームアシスト法で非還元性ガスを照射すること
により、上記酸化物系超電導体の超電導特性を向上させ
ることができる。Therefore, in this case as well, the superconducting properties of the oxide-based superconductor can be improved by irradiating non-reducing gas with the ion beam assist method during film formation, as in the above example.
さらにまた、この例では、最終的に得られる酸化物超電
導体をＡ−Ｂ−Ｃｕ−０系のものとしたが、Ａ−Ｂ−Ｃ
ｕ−０−Ｘ系（但し、ＸはＦ、ＣＣ。Furthermore, in this example, the oxide superconductor finally obtained was of the A-B-Cu-0 system, but the A-B-C
u-0-X system (X is F, CC.
Ｂｒ等のハロゲン族元素の１種あるいは２種以上を表す
。）の酸化物超電導体またはその前駆体も製造できる。Represents one or more halogen group elements such as Br. ) oxide superconductors or their precursors can also be produced.
第２図に示した製造装置３を用い、真空蒸着法とイオン
ビームアシスト法とを組合わせた方法により板状の基体
表面にＹ−Ｂａ−Ｃｕ−０系の超電導体からなる膜体２
を形成した。以下、実施例を示す。上記の基体ｌには安
定化ジルコニア（ＺｒＯ，）製のものを使用するととも
に、蒸着材料にはＹ元素の単体、Ｂａ元素の単体、及び
Ｃｕ元索の単体を用いた。これら３種類の蒸着材を三つ
のるつぼ６．６．６にそれぞれ別々に入れて、３源同時
に電子ビーム蒸着をし得るようにした。そして、成膜時
の雰囲気を１００％酸素ガスからなるものとし、その圧
力を０．２５ Ｐａとした。また、非還元性ガスイオン
としてアルゴンガスイオンを用い、そのイオン源４のイ
オン電流密度をＩｉＡ／ｃ＋ｗ”、加速電圧を２００Ｖ
に設定した。さらに、上記基体１の温度（基体温度）を
６００℃とした。Using the manufacturing apparatus 3 shown in FIG. 2, a film body 2 made of a Y-Ba-Cu-0 based superconductor is formed on the surface of a plate-shaped substrate by a method combining a vacuum evaporation method and an ion beam assist method.
was formed. Examples are shown below. The above-mentioned substrate 1 was made of stabilized zirconia (ZrO), and the vapor deposition materials were a simple substance of Y element, a simple substance of Ba element, and a simple substance of Cu element. These three types of evaporation materials were placed separately in three crucibles 6.6.6 so that electron beam evaporation could be performed simultaneously with three sources. The atmosphere during film formation was 100% oxygen gas, and the pressure was 0.25 Pa. In addition, argon gas ions are used as non-reducing gas ions, the ion current density of the ion source 4 is IiA/c+w'', and the acceleration voltage is 200V.
It was set to Further, the temperature of the substrate 1 (substrate temperature) was set to 600°C.
このような条件の下にアルゴンガスイオンを照射しなが
ら、約２時間かけて厚さ約１μ屑の膜体２を形成した。Under these conditions and while irradiating with argon gas ions, a film body 2 having a thickness of about 1 μm was formed over about 2 hours.
この膜体２の結晶性を調べたところ、Ｃ軸が基体１の垂
直方向に整然と配列していることが確認された。次いで
、この膜体２を温度３００℃の酸素雰囲気中で熱処理を
行いＹ−Ｂａ−Ｃｕ−０系の超電導体からなる膜体２を
製造した。この膜体２の臨界温度（Ｔ ｃ）を測定した
ところ、８８にという結果が得られた。なお、基体温度
を７００℃として形成した膜体のＴｃは８９にであった
。When the crystallinity of this film body 2 was examined, it was confirmed that the C-axis was regularly aligned in the vertical direction of the base body 1. Next, this film body 2 was heat-treated in an oxygen atmosphere at a temperature of 300° C. to produce a film body 2 made of a Y-Ba-Cu-0 based superconductor. When the critical temperature (Tc) of this film body 2 was measured, a result of 88 was obtained. Note that the Tc of the film formed at a substrate temperature of 700° C. was 89.
これに対し、比較のため、従来の真空蒸着装置を用いて
膜体２を形成した。この場合の成膜条件が上記実施例の
条件と異なるところは、アルゴンガスイオンの照射が行
われない点である。On the other hand, for comparison, a film body 2 was formed using a conventional vacuum evaporation apparatus. The film forming conditions in this case differ from those in the above embodiments in that argon gas ion irradiation is not performed.
このような条件で得られた成膜後の膜体２の物性を調べ
たところ、基体温度６００℃では結晶化せずアモルファ
ス状態となっていた。また、熱処理後の膜体２の電気特
性を調べたところ、半導体的な挙動を示し、超電導特性
を示さなかった。When the physical properties of the film body 2 after film formation obtained under these conditions were examined, it was found that at a substrate temperature of 600° C., it did not crystallize and was in an amorphous state. Further, when the electrical properties of the film body 2 after the heat treatment were examined, it showed semiconductor-like behavior and did not exhibit superconducting properties.
以上説明したように、この発明の製造方法によれば、酸
化物系超電導体あるいはその前駆体を成膜法により形成
する際に、非還元性ガスイオンなどを加速して照射しつ
つ形成するようにしたので、酸化物系超電導体あるいは
その前駆体を構成する各元素が適度に活性化されて、結
晶のＣ軸が基体の垂直方向に配向した酸化物系超重導体
あるいはその前駆体からなる膜体を得ることができる。As explained above, according to the manufacturing method of the present invention, when an oxide-based superconductor or its precursor is formed by a film-forming method, it is formed while being irradiated with accelerated non-reducing gas ions. As a result, each element constituting the oxide superconductor or its precursor is appropriately activated, resulting in a film made of the oxide superconductor or its precursor in which the C-axis of the crystal is oriented in the vertical direction of the substrate. You can get a body.
したがって、全体が均質かつ強固で、−段と良好な超電
導特性を示す酸化物系超電導体を製造できる。Therefore, it is possible to produce an oxide-based superconductor that is homogeneous and strong as a whole and exhibits much better superconducting properties.
また、この製造方法によれ゛ば、従来例に比べて結晶中
への酸素の導入量が多い酸化物系超電導体の前駆体を製
造することができ°るので、この前駆体によれば、酸素
雰囲気中での低温熱処理により最終物質（酸化物超電導
体からなる膜体）を製造することができる。したがって
、以上の製造方法によれば、さらに、次のような優れた
効果を得ることができる。すなわち、従来法と異なり、
成膜時の基体温度及び成膜後の熱処理温度を低温に設定
することができるので、（１）基体と膜体とが高温で反
応し合う不都合もなく、この点においても膜体２の超電
導特性を良好なものとすることができる。（２）基体の
形成材料として比較的安価な材料を選ぶことができる。Furthermore, according to this manufacturing method, it is possible to manufacture a precursor of an oxide-based superconductor in which a larger amount of oxygen is introduced into the crystal than in the conventional example. The final material (film body made of oxide superconductor) can be manufactured by low-temperature heat treatment in an oxygen atmosphere. Therefore, according to the above manufacturing method, the following excellent effects can be obtained. In other words, unlike the conventional method,
Since the substrate temperature during film formation and the heat treatment temperature after film formation can be set to low temperatures, (1) there is no inconvenience in which the substrate and the film react with each other at high temperatures; The characteristics can be improved. (2) A relatively inexpensive material can be selected as the material for forming the base.
（３）微細加工部分に欠陥が生じにくいため、例えばジ
ョセフソン素子など、微細な超電導デバイスを一段と良
好に製造することができる。(3) Since defects are less likely to occur in microfabricated parts, microscopic superconducting devices such as Josephson elements can be manufactured even better.
第１図は、この発明の製造方法によって製造された酸化
物系超電導体の一例を示す概略断面図、第２図は、この
発明の製造方法に好適に用いられる製造装置の一例を示
す概略構成図である。
２・・・・・・膜体（酸化物系超電導体またはその前駆
体）、
４・・・・自イオン源。FIG. 1 is a schematic cross-sectional view showing an example of an oxide-based superconductor manufactured by the manufacturing method of the present invention, and FIG. 2 is a schematic configuration showing an example of a manufacturing apparatus suitably used in the manufacturing method of the present invention. It is a diagram. 2...Membrane body (oxide-based superconductor or its precursor), 4...Self-ion source.
Claims (1)
を成膜法により形成する際に、非還元性ガスを加速して
照射しつつ形成することを特徴とする酸化物系超電導体
の製造方法。A method for producing an oxide superconductor, characterized in that when forming an oxide superconductor or a precursor of an oxide superconductor by a film formation method, the formation is performed while accelerating and irradiating a non-reducing gas. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62283628A JPH01124919A (en) | 1987-11-10 | 1987-11-10 | Manufacture of oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62283628A JPH01124919A (en) | 1987-11-10 | 1987-11-10 | Manufacture of oxide superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01124919A true JPH01124919A (en) | 1989-05-17 |
Family
ID=17667976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62283628A Pending JPH01124919A (en) | 1987-11-10 | 1987-11-10 | Manufacture of oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01124919A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03279294A (en) * | 1990-03-29 | 1991-12-10 | Mitsubishi Materials Corp | Growth of epitaxial layer |
-
1987
- 1987-11-10 JP JP62283628A patent/JPH01124919A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03279294A (en) * | 1990-03-29 | 1991-12-10 | Mitsubishi Materials Corp | Growth of epitaxial layer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4950642A (en) | Method for fabricating superconducting oxide thin films by activated reactive evaporation | |
| EP0285030A2 (en) | Process for producing superconducting thin films | |
| WO1998017846A1 (en) | Process for preparing polycrystalline thin film, process for preparing oxide superconductor, and apparatus therefor | |
| US4925829A (en) | Method for preparing thin film of compound oxide superconductor by ion beam techniques | |
| US4874741A (en) | Non-enhanced laser evaporation of oxide superconductors | |
| CA1322514C (en) | Thin film of single crystal of lna_cu_o___ having three-layered perovskite structure and process for producing the same | |
| JPH01124919A (en) | Manufacture of oxide superconductor | |
| JP5145109B2 (en) | Method for producing polycrystalline thin film and method for producing oxide superconducting conductor | |
| JPH01261204A (en) | Production of oxide based superconductor | |
| JPH0238302A (en) | Formation of superconducting thin film | |
| JP2639544B2 (en) | Single crystal thin film of LaA Lower 2 Cu 3 Lower O 7 Lower 3 x with three-layer perovskite structure and LaA Lower 2 Cu Lower 3 O Lower 7 Lower 7 x thin film manufacturing method | |
| JPH01201008A (en) | Production of thin film of oxide superconductor | |
| JP2611332B2 (en) | Manufacturing method of thin film superconductor | |
| JP2742418B2 (en) | Method for producing oxide superconducting thin film | |
| JPH01259582A (en) | Manufacture of oxide superconductive thin film | |
| JPH01183176A (en) | Manufacture of thin superconducting film | |
| DE68909644T2 (en) | Oxide superconductor. | |
| JPH01161628A (en) | Formation of oxide superconducting thin film | |
| JP2525852B2 (en) | Preparation method of superconducting thin film | |
| JP2501616B2 (en) | Preparation method of superconducting thin film | |
| JPH01109614A (en) | Manufacture of oxide superconductor | |
| JP2919956B2 (en) | Superconducting member manufacturing method | |
| JP2835235B2 (en) | Method of forming oxide superconductor thin film | |
| JP2501614B2 (en) | Preparation method of superconducting thin film | |
| JP2501615B2 (en) | Preparation method of superconducting thin film |